US3907710A - Hollow ceramic pellets for catalyst support - Google Patents

Hollow ceramic pellets for catalyst support Download PDF

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US3907710A
US3907710A US352165A US35216573A US3907710A US 3907710 A US3907710 A US 3907710A US 352165 A US352165 A US 352165A US 35216573 A US35216573 A US 35216573A US 3907710 A US3907710 A US 3907710A
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catalyst
support
surface area
palladium
extrudates
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Christian Bent Lundsager
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WR Grace and Co Conn
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WR Grace and Co
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Priority to US352165A priority Critical patent/US3907710A/en
Priority to CA196,216A priority patent/CA989808A/en
Priority to IT21408/74A priority patent/IT1007921B/it
Priority to FR7413241A priority patent/FR2226256B1/fr
Priority to DE2418403A priority patent/DE2418403A1/de
Priority to GB1683274A priority patent/GB1474553A/en
Priority to JP49042785A priority patent/JPS5051991A/ja
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Publication of US3907710A publication Critical patent/US3907710A/en
Assigned to W.R. GRACE & CO.-CONN. reassignment W.R. GRACE & CO.-CONN. MERGER (SEE DOCUMENT FOR DETAILS). EFFECTIVE DATE: MAY 25, 1988 CONNECTICUT Assignors: GRACE MERGER CORP., A CORP. OF CONN. (CHANGED TO), W.R. GRACE & CO., A CORP. OF CONN. (MERGED INTO)
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63408—Polyalkenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28—Construction of catalytic reactors
    • F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
    • F01N3/2825—Ceramics
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
    • Y10S502/524—Spinel

Definitions

  • FIG 2 HOLLOW CERAMIC PELLETS FOR CATALYST SUPPORT BACKGROUND OF THE INVENTION
  • the catalyst is in one or two forms. In one system the catalyst composition is distended on a monolithic structure that is generally a ceramic cylinder that has a series of channels extending the full length of the monolith structure.
  • These'monolithic catalysts structures are advantageous in that the surface area per unit weight is very high. They have the disadvantage of frequently being fragile and subject to breakage or thermal damage and are difficult to make.
  • the alternative structures are pellets, pills, extrudates, etc. These are solid bodies that are generally a maximum of one inch in thelongest dimension. These pellets, pills, extrudates, etc., have the advantage of generally satisfactory thermal stability, however, their surface area per unit weight leaves much to be desired.
  • the catalyst structures of our invention can be prepared from a starting material consisting of a ceramic powder such as alumina, cordierite, mullite, spinel, etc., a polyolefin, and a plasticizer.
  • the polyolefin used is the high molecular weight polyolefin, more specifically, a polyolefin having a molecular weight of at least 150,000.
  • This polyolefin is a good binder for the cordierite or other filler material and can tolerate high filler loading without becoming brittle when a plasticizer is present. It is important that the polyolefin be a high molecular weight polymer since low molecular weight polymers, (molecular weight 60,000 to 100,000) yield brittle products at relatively low filler concentrations.
  • the polymer and filler are blended together and a plasticizer is incorporated into these blends to provide good flow characteristics and facilitate mixing without causing excessive loss of flexibility.
  • the plasticizer are essential for retaining the 'desirable performance of the binder system.
  • the composition consists of 5-70 volume percent polyolefin, 50-80 volume percent plasticizer, and 45-80 volume percent cordierite or other ceramic powder.
  • the preferred ranges are 5-50 volume percent polyolefin -60 volume percent plasticizer, and 20-50 volume percent of the ceramic powder material.
  • the polyolefin used for preparing our novel product is a high molecular weight polyethylene or copolymers such as ethylene-butene copolymers or other polyolefins having a standard load (2,160 grams) melt index of 0.0 a high load (21,600 grams) melt index of 1.8, a density of 0.93 to 0.97, a viscosity of about 4 measured as 0.02 grams of polymer and grams of decalin at C.
  • the melt index is a polyolefin flow at standard conditions of temperature and pressure to an orifice of definite diameter and length as described in ASTMD 1,238 ATS Condition F (Measured Flow Rates of Thermoplastics by Extrusion Plastometer).
  • the rate of extrusion in grams per 10 minutes is the melt index and is used to indicate the average molecular weight of the polymer. The lower the molecular weight of the polymer, the more rapidly it extrudesand, therefore. the melt index increase as the molecular weight decreases.
  • HLMI High Load Melt Index
  • plasticizers give satisfactory results and it is advantageous to use a plasticizer that is soluble in water.
  • a water soluble plasticizer the extraction will be more economical, due to the low cost and relative safety of water in comparison with that of organic solvents.
  • the extraction process will also be much safer as there are no fire or toxicity hazards encountered.
  • water insoluble plasticizers examples include: dibutyl sebacate, diisododecyl phthalate, zinc stearate, stearic acid polyethylene glycol distearate, epoxidized vegetable oil, tricresyl phosphate, petroleum oil, paraffin oil, wax, hydrocarbon resin, asphalt, eicosane, tall oil, linseed oil, and oxidized polyethylene wax.
  • water soluble plasticizers examples include diethylene glycol, propylene glycol, dipropylene glycol, glycerin, glycerol monoacetate, trimethylene glycol, tetramethylene glycol, triethyl phosphate, polyvinyl alcohol and polyvinyl pyrrolidone. It is also possible to make the product of this invention using various combinations of the above mentioned plasticizers such as the usage of water soluble and a water insoluble plasticizer with the ceramic powder material and high density polyethylene.
  • the ceramic powdered materials used in the preparation of our novel catalyst support are well known.
  • the preferred ceramic powder is cordierite, however, mullite, spinel, and alumina also give satisfactory results.
  • the solvent used to extract the plasticizer depends on the type of plasticizer used.
  • suitable organic solvents include, hexane, heptane, benzene, chlorinated solvents such as carbon tetrachloride, trichloroethylene and perchloroethylene, for example, petroleum ether, diethyl ether, etc.
  • the mixture from which our novel catalyst support is prepared is normally compounded by mixing the high molecular weight polyolefin, the ceramic powdered material and the plasticizer in any of the commercially available mixers, such as a dough mixer for example. However, in some cases the ceramic powders and plasticizers are stirred together at room temperature in a volatile solvent which is evaporated before the material is combined with the polyethylene.
  • the polyolefinceramic powder-plasticizer dry blend is then mixed in a suitable commercially available mixer such as a Brabender Plastograph.
  • the preferred mixing procedure is to feed the ceramic powder, polyolefin polymer, and
  • plasticizer as separate streams to a compounding device where the components are heated to a tempera ture of 300-500F and working the mix until it is uniform.
  • the time and temperature depend on the device used. However, the compounding is usually completed in l to minutes.
  • the product is cooled and reduced to a convenient size for feeding to a conventional extruder.
  • the essential feature of our invention results from the extrusion step.
  • the pellets we prepare are hollow cylinders with internal reinforcingribs to improve the crush strength and increase the surface area.
  • the product is prepared by extruding a cordierite-polyolefin-plasticizer mix into a reinforced tube using a specially designed die and then cutting the tube to short lengths followed by extraction of the plasticizer and firing.
  • the finished extruded shape can also be made by extrusion simultaneously with the hot compounding step.
  • FIG. 1 shows the exterior of an extrudate with four internal ribs
  • FIG. 2 is a cross sectional view taken along the line 22 of FIG. 1.
  • FIG. 3 shows the exterior of an extrudate with six internal ribs.
  • FIG. 4 is a cross sectional view taken along line 4-4 of FIG. 3.
  • the product of our invention has several advantages: (1) the extrudates have a surface area of at least 50% greater than a hollow tube of the same diameter, approximately 3 times greater than the surface area of solid particles, (2) the extrudates have about one-half the weight of solid particles, (3) the extrudates of our invention heat up faster in use than solid pellets, (4) the extrudates of our invention exhibit a lower pressure drop than solid pellets in a catalytic system for treating exhaust gases.
  • the extrudates are normally cut to the desired length, normally about equal to its diameter. It is most convenient to cut the extrudates at-this stage rather than after the extraction of the plasticizer and final firing step, although it is obviousthese'steps can be carried out after extraction and firing as well.
  • the extraction step is conventional.
  • the extrudates are contacted with an inorganic or organic solvent for the plasticizer used.
  • the representative solvents for extracting organic plasticizers such as petroleum oil for example include trichloroethylene, tetrachloroethylene, carbon tetrachloride, methylene chloride, tetrachloroethane, hexane, benzene, petroleum ether,
  • Illustrative solvents useful for extracting water soluble plasticiziers include polyethylene glycol, water, ethanol, methanol and acetone.
  • the extraction temperature can range from room temperature (25C) to the melting point of the polyolefin component, so long as the polyolefin does not dissolve.
  • the period of time required to carry out the extraction will vary depending on the temperature used and the nature of the plasticizer being extracted.
  • the structure is heated to above the degradation temperature of the thermoplastic to burn off the polyolefin.
  • a degradation temperature in the range of at least 240 to 260C is preferred to initiate degradation.
  • the structure begins to turn black and at about 700C the structure begins to turn white indicating that the thermoplastic has entirely burned off.
  • the temperature is increased to'that at which the particular powder sinters into a monolithic structure while retaining its microporosity.
  • (cordierite) a temperature of about l,3001,450C is recommended. The temperature is maintained at the sintering point for about 2 hours and the extrudates are then allowed to cool slowly to room temperature. The cooling time is generally around 3 to 4 hours.
  • the resulting ceramic extrudates appear identical in shape to the original extrudates except that there is a slight linear shrinkage in the order of 2l 5 percent, depending on the ceramic.
  • the shrinkage is only about 25 percent when cordierite is the ceramic.
  • extrudates of our invention were evaluated as a catalyst support by preparing a slip containing the catalytically components and coating the extrudates with this slip. The excess slip is removed and the extrudates dried and calcined.
  • the auto exhaust catalyst of my invention is distended on a reinforced porous tubular ceramic support having a diameter of from about 3 to 12 mm and a length of about equal to the diameter said support characterized by:
  • the tubular ceramic support is coated with about 5 to 10 wt. percent of an alumina containing 5 to 20 percent ceria, and about 0.02 to 0.8 wt. percent of platinum, palladium or mixtures thereof, based on the weight of the catalyst.
  • the finished catalyst was evaluated using the procedure described in detail in the Federal Register of July, 1970 as modified by the instructions in the Federal Register of July, 1971.
  • this test is designed to determine the hydrocarbon, carbon monoxide, the oxides of nitrogen gas emissions while simulating the average trip in an urban area of 7% miles from a cold start.
  • the test consists of an engine start up and vehicle operation on a chassis dynamomter to a specified driving schedule consisting of a total of 1,371 seconds.
  • a proportionate part of the diluted gas emissions is collected continuously for a subsequent analysis using the constant volume sampler technique.
  • the dynamometer run consists of two tests, a cold start test after a minimum of 12 hours soak, and a hot start test with a 10 minute soak between the two tests. Engine start up and operation over the first 505 seconds of the driving schedule completes the hot start test.
  • Engine emissions are diluted with air to a constant volume and a portion sampled during .each test.
  • the composite samples are collected in bags and analyzed for hydrocarbons, carbon monoxide, carbon dioxide, and oxides of nitrogen.
  • Parallel samples, of diluted air are similarly analyzed for hydrocarbons, carbon monoxide, and oxides of nitrogen.
  • the gasoline used in the test is octane gasoline containing less than 0.5 grams of organic leads per gal- Ion.
  • the gas samples are analyzed for hydrocarbons by a flame ionization detector. Carbon monoxide and carbon dioxide are determined by nondispersive infrared analysis. Nitrogen oxides are analyzed by nondispersive infrared and ultra violet analysis.
  • EXAMPLE 1 A batch of hollow pellets were prepared by extruding a cordierite-polyethylene-mineral oil mixture in a commercially available extruder using a die that produced an extrudate having six internal ribs similar in cross section to the extrudate shown in FIG. 2.
  • the extrudates were one-fourth inch in diameter and were cut into pellets about one-fourthinch long.
  • the plasticizer was removed by immersing the pellets in trichloroethylene at about 25C for 2 hours.
  • the pellets were dried and heated to about 240 to 700C over a period of 2 hours to burn off the polyethylene.
  • the pellets were then sintered at about 1,400C for 2 hours.
  • the hollow pellets were cooled to room temperature and found to have a crush strength of 12 pounds measured on the diameter.
  • a slip was prepared by mixing 606 grams of alumina containing 6% ceria, 250 grams of cerium nitrate (Ce(- NO .6H O) 2,072 grams of water, 5 grams of nitric acid and 3.06 grams of platinum ammonium nitrate (Pt(NH (NO).
  • the slip was prepared by mixing the components in a high shear stirrer.
  • the coated extrudates were dried for 3 hours at 250F and then calcinedfor 2 hours at l,200F.
  • the extrudates were then reimpregnated with a solution of palladium nitrate (Pd( N0 by immersing the extrudates in three liters of a solution of the palladium nitrate EXAMPLE 3
  • the catalyst prepared according to the process described in Example 1 was compared to a solid pelleted catalyst containing the same level of noble metals. The evaluation was carried out using the procedure described in the Federal Register referred to above. The results are set out in Table 1 below: i
  • EXAMPLE 4 The catalyst was evaluated in a bench test designed to simulate the exhaust gas composition and heat up conditions experienced by catalysts in the initial part of the actual chassis dynamometer run described in the Federal Register'reference. The test approximates the environment the catalyst will experience during the allimportant cold start segment of the chassis dynamometer test which accounts for a substantial portion of the total carbon monoxide emitted.
  • the catalyst prepared according to the process described previously and a catalyst prepared to contain the same level of catalytic agents on solidpellets were evaluated. The evaluation was carried outzby filling the reactor to 13 cc of the reactor volume. The total gas rate was regulated to achieve a gas hourly space velocity of approximately 38,000.
  • the simulatedexhaust gas contained 250 parts per million hexane, 0.5 volume percent oxygen, 10 volume percent water vapor, 500 parts per million nitrogen oxide, 10 volume percent carbon monoxide with the balance made up by nitrogen.
  • the gas mixture was preheated so that the inlet temperature to the bed of catalyst was 600F.
  • the bed began to heat up in a similar manner similar to heat up in an actual catalytic device on an automobile.
  • catalytic oxidation of the carbon'monoxide and hydrocarbonsand reduction of the nitrogen oxide and the steam commenced and the temperature increased at an accelerated rate due to the heat of reaction.
  • the catalyst performance was measured by determining the carbon monoxide index of the catalyst of Example 1 and comparing this index with the car bon monoxide index of the catalyst on solid pellets. This data is presented in Table 2 below:
  • the carbon monoxide index compares the conversion of. carbon monoxide of the catalyst being tested withthe conversion of carbon monoxide by a reference catalysthA low carbon monoxide index indicates high catalytic activity. 7 .What is elaimed-is:.
  • a catalyst for converting carbon monoxide, hydrocarbons and nitrogen oxides in auto exhaust gases to innocuous entities consisting essentially of platinum or palladium distended as a coating of alumina containing .jabo ut 5. to 20 weight percent ceria on a porous tubular .tio.
  • tubular ceramic support is coated with about 5 to 10 weight percent of an alumina containing about 0.02 to ).O8 weight percent, platinum or palladium based on thewei ght of the catalyst.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Structural Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Biomedical Technology (AREA)
  • Toxicology (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Porous Artificial Stone Or Porous Ceramic Products (AREA)
US352165A 1973-04-18 1973-04-18 Hollow ceramic pellets for catalyst support Expired - Lifetime US3907710A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US352165A US3907710A (en) 1973-04-18 1973-04-18 Hollow ceramic pellets for catalyst support
CA196,216A CA989808A (en) 1973-04-18 1974-03-28 High surface area catalyst support
IT21408/74A IT1007921B (it) 1973-04-18 1974-04-12 Catalizzatore per gas di scarico di automobili e supporto per cata lizzatore con elevata area super ficiale
DE2418403A DE2418403A1 (de) 1973-04-18 1974-04-16 Keramischer koerper zur verwendung als katalysatortraeger sowie verfahren zu dessen herstellung
FR7413241A FR2226256B1 (fr) 1973-04-18 1974-04-16
GB1683274A GB1474553A (en) 1973-04-18 1974-04-17 Process of preparing a ceramic structure suitable for use as a catalyst support
JP49042785A JPS5051991A (fr) 1973-04-18 1974-04-18

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JP (1) JPS5051991A (fr)
CA (1) CA989808A (fr)
DE (1) DE2418403A1 (fr)
FR (1) FR2226256B1 (fr)
GB (1) GB1474553A (fr)
IT (1) IT1007921B (fr)

Cited By (23)

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Publication number Priority date Publication date Assignee Title
DE2719543A1 (de) * 1976-05-07 1977-12-01 Ceraver Keramikkoerper zur aufnahme eines katalysators
US4089941A (en) * 1975-10-22 1978-05-16 A.P.C. (Azote Et Produits Chimiques) Catalysts & Chemicals Europe Societe Steam reformer process for the production of hydrogen
US4260524A (en) * 1979-05-24 1981-04-07 Sumitomo Aluminium Smelting Company, Limited Hollow catalyst carrier and hollow catalyst made of transition-alumina and process for production thereof
US4267086A (en) * 1976-01-07 1981-05-12 Ford Motor Company Sacraficial binders for molding particulate solids
US4460704A (en) * 1980-06-15 1984-07-17 Imperial Chemical Industries Plc Catalyst for the production of hydrogen
US4474731A (en) * 1983-03-28 1984-10-02 International Business Machines Corporation Process for the removal of carbon residues during sintering of ceramics
US4510263A (en) * 1983-10-17 1985-04-09 W. R. Grace & Co. Catalyst with high geometric surface area alumina extrudate and catalyst with high geometric surface area
US4510261A (en) * 1983-10-17 1985-04-09 W. R. Grace & Co. Catalyst with high geometric surface area
US4510262A (en) * 1983-10-17 1985-04-09 W. R. Grace & Co. Doubly promoted catalyst with high geometric surface area
US4541996A (en) * 1983-10-17 1985-09-17 W. R. Grace & Co. Process for utilizing catalyst with high geometric surface area
US4541995A (en) * 1983-10-17 1985-09-17 W. R. Grace & Co. Process for utilizing doubly promoted catalyst with high geometric surface area
US4661468A (en) * 1982-07-13 1987-04-28 Cpus Corporation Catalyst for treatment and cleaning of exhaust fumes
US4705767A (en) * 1986-12-15 1987-11-10 W. R. Grace & Co. Sulfactants in acid-peptized catalyst compositions
AU571267B2 (en) * 1983-10-17 1988-04-14 W.R. Grace & Co.-Conn. Alumina support extrudate and catalyst with high geometric surface area
US4810463A (en) * 1986-09-12 1989-03-07 Syracuse University Process for forming sintered ceramic articles
US4826799A (en) * 1988-04-14 1989-05-02 W. R. Grace & Co.-Conn. Shaped catalyst and process for making it
WO1996041110A1 (fr) 1995-06-07 1996-12-19 W.R. Grace & Co.-Conn. Particules profilees utilisees comme agents caloporteurs dans dessystemes d'oxydation thermique a recuperation
US6302188B1 (en) 1998-04-28 2001-10-16 Megtec Systems, Inc. Multi-layer heat exchange bed containing structured media and randomly packed media
US6558533B2 (en) 2001-04-13 2003-05-06 W.R. Grace & Co.-Conn Process for sulfur removal from hydrocarbon liquids
US6573213B1 (en) * 1999-07-16 2003-06-03 Degussa Ag Metal catalysts
US6699562B2 (en) 2002-02-28 2004-03-02 Saint-Gobain Corporation Ceramic packing element
US20040170804A1 (en) * 2002-02-28 2004-09-02 Niknafs Hassan S. Ceramic packing element with enlarged fluid flow passages
US20070219279A1 (en) * 2006-03-03 2007-09-20 Leveson Philip D Method for enhancing catalyst selectivity

Families Citing this family (10)

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US4089941A (en) * 1975-10-22 1978-05-16 A.P.C. (Azote Et Produits Chimiques) Catalysts & Chemicals Europe Societe Steam reformer process for the production of hydrogen
US4267086A (en) * 1976-01-07 1981-05-12 Ford Motor Company Sacraficial binders for molding particulate solids
DE2719543A1 (de) * 1976-05-07 1977-12-01 Ceraver Keramikkoerper zur aufnahme eines katalysators
US4260524A (en) * 1979-05-24 1981-04-07 Sumitomo Aluminium Smelting Company, Limited Hollow catalyst carrier and hollow catalyst made of transition-alumina and process for production thereof
US4460704A (en) * 1980-06-15 1984-07-17 Imperial Chemical Industries Plc Catalyst for the production of hydrogen
US4661468A (en) * 1982-07-13 1987-04-28 Cpus Corporation Catalyst for treatment and cleaning of exhaust fumes
US4474731A (en) * 1983-03-28 1984-10-02 International Business Machines Corporation Process for the removal of carbon residues during sintering of ceramics
US4510263A (en) * 1983-10-17 1985-04-09 W. R. Grace & Co. Catalyst with high geometric surface area alumina extrudate and catalyst with high geometric surface area
US4510262A (en) * 1983-10-17 1985-04-09 W. R. Grace & Co. Doubly promoted catalyst with high geometric surface area
US4541996A (en) * 1983-10-17 1985-09-17 W. R. Grace & Co. Process for utilizing catalyst with high geometric surface area
US4541995A (en) * 1983-10-17 1985-09-17 W. R. Grace & Co. Process for utilizing doubly promoted catalyst with high geometric surface area
US4510261A (en) * 1983-10-17 1985-04-09 W. R. Grace & Co. Catalyst with high geometric surface area
AU571267B2 (en) * 1983-10-17 1988-04-14 W.R. Grace & Co.-Conn. Alumina support extrudate and catalyst with high geometric surface area
US4810463A (en) * 1986-09-12 1989-03-07 Syracuse University Process for forming sintered ceramic articles
US4705767A (en) * 1986-12-15 1987-11-10 W. R. Grace & Co. Sulfactants in acid-peptized catalyst compositions
US4826799A (en) * 1988-04-14 1989-05-02 W. R. Grace & Co.-Conn. Shaped catalyst and process for making it
WO1996041110A1 (fr) 1995-06-07 1996-12-19 W.R. Grace & Co.-Conn. Particules profilees utilisees comme agents caloporteurs dans dessystemes d'oxydation thermique a recuperation
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US6747180B2 (en) * 1999-07-16 2004-06-08 Degussa Ag Metal catalysts
US6558533B2 (en) 2001-04-13 2003-05-06 W.R. Grace & Co.-Conn Process for sulfur removal from hydrocarbon liquids
US6699562B2 (en) 2002-02-28 2004-03-02 Saint-Gobain Corporation Ceramic packing element
US20040170804A1 (en) * 2002-02-28 2004-09-02 Niknafs Hassan S. Ceramic packing element with enlarged fluid flow passages
US6889963B2 (en) 2002-02-28 2005-05-10 Saint-Gobain Norpro Corporation Ceramic packing element
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Also Published As

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JPS5051991A (fr) 1975-05-09
CA989808A (en) 1976-05-25
DE2418403A1 (de) 1974-10-31
FR2226256B1 (fr) 1977-10-07
FR2226256A1 (fr) 1974-11-15
GB1474553A (en) 1977-05-25
IT1007921B (it) 1976-10-30

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